Production of substituted phenylene dibenzoate internal electron donor and procatalyst with same

ABSTRACT

The present disclosure is directed to the production of substituted phenylene aromatic diesters and 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate (or “BMPD”) in particular. The processes disclosed herein produce a liquid BMPD product. The liquid BMPD product unexpectedly creates production efficiencies by reducing the number of production steps, reducing the amount and/or number of reagents required for BMPD production. The liquid BMPD product may also be utilized in procatalyst production yielding similar production efficiencies. The procatalyst composition is subsequently used for olefin polymerization.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. patent application Ser.No. 13/220,910, filed Aug. 30, 2011, the disclosure of which isincorporated herein by reference.

BACKGROUND

The present disclosure relates to the production of substitutedphenylene aromatic diesters, procatalysts containing same, and polymersproduced with the procatalysts.

Substituted phenylene aromatic diesters are used as internal electrondonors in the preparation of procatalyst compositions for the productionof olefin-based polymers. In particular, Ziegler-Natta catalystscontaining 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate as internalelectron donor show high catalyst activity and high selectivity duringpolymerization. In addition, such catalysts produce olefin-based polymer(such as propylene-based polymer) with high isotacticity and medium tobroad molecular weight distribution.

The art recognizes the need for olefin-based polymers andpropylene-based polymers with improved properties. Desired are multipleand/or alternate synthesis pathways for the production of substitutedphenylene aromatic diester to ensure a cost-effective, and reliablesupply of the same.

SUMMARY

The present disclosure is directed to the production of substitutedphenylene aromatic diesters and 5-tert-butyl-3-methyl-1,2-phenylenedibenzoate (or “BMPD”) in particular. The BMPD is subsequently utilizedas an internal electron donor in the synthesis of a procatalystcomposition. The resultant procatalyst composition is used for thepolymerization of olefin-based polymer. The term “olefin-based polymer”is a polymer containing, in polymerized form, a majority weight percentof an olefin, for example ethylene or propylene, based on the totalweight of the polymer. Nonlimiting examples of olefin-based polymersinclude ethylene-based polymers and propylene-based polymers.

A precursor, namely 5-tert-butyl-3-methylcatechol, is used in theproduction process. The present processes simplify production of theBMPD, and/or simplify the production of the procatalyst compositionyielding economic savings, a reduction in production resources(reduction in energy, equipment, manpower, and/or production reagents).These advantages promote large-scale and efficient production of (1)BMPD, (2) procatalyst composition with BMPD, and (3) olefin polymer withBMPD.

The present disclosure provides a process. In an embodiment, a processis provided and includes combining, under reaction conditions in areaction mixture, 5-tert-butyl-3-methyl catechol (BMC), triethylamine,benzoyl chloride, and a water insoluble solvent. The process alsoincludes forming a liquid 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate(BMPD) product in the reaction mixture.

In an embodiment, the water insoluble solvent is selected from toluene,ethyl acetate, chlorobenzene, orthochlorotoluene, and combinationsthereof.

The present disclosure provides another process. In an embodiment, aprocess is provided an includes combining, under reaction conditions ina first reaction mixture, a water insoluble solvent, BMC, triethylamine,and benzoyl chloride to form a liquid BMPD product. The process includesadding, under reaction conditions, the liquid BMPD product to a secondreaction mixture. The second reaction mixture includes a procatalystprecursor, a halogenating agent, and chlorobenzene. The process furtherincludes forming a solid procatalyst composition.

In an embodiment, the water insoluble solvent is selected from toluene,ethyl acetate, orthochlorotoluene, chlorobenzene, and combinationsthereof.

The present disclosure provides another process. In an embodiment, aprocess is provided and includes forming a liquid BMPD product andadding, under reaction conditions, the liquid BMPD product to aprocatalyst precursor, a halogenating agent, and chlorobenzene to form asolid procatalyst composition. The process includes contacting anolefin, under polymerization conditions, with the solid procatalystcomposition, a cocatalyst, and an external electron donor; and formingan olefin-based polymer.

In an embodiment, the process includes forming the liquid BMPD productin a water insoluble solvent selected from toluene, ethyl acetate,orthochlorotoluene, chlorobenzene, and combinations thereof.

An advantage of the present disclosure is an improved process for theproduction of 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate (BMPD), asubstituted phenylene aromatic diester.

An advantage of the present disclosure is a process for producing BMPDthat reduces process steps thereby increasing production efficiency.

An advantage of the present disclosure is the provision of aphthalate-free catalyst composition and a phthalate-free olefin-basedpolymer produced therefrom.

An advantage of the present disclosure is an improved process for theproduction of procatalyst composition containing BMPD.

An advantage of the present disclosure is a process for producingprocatalyst composition containing BMPD that reduces the number ofprocess steps and/or reduces the number/amount of reagents required toproduce the procatalyst composition.

An advantage of the present disclosure is a process for large scaleproduction of BMPD.

An advantage of the present disclosure is an environmentally-safe,non-toxic production process for BMPD.

An advantage of the present disclosure is a simple, time-effective,and/or cost-effective purification process for BMPD.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flowchart showing a process for producing BMPD.

FIG. 2 is a flowchart showing a process for producing BMPD in accordancewith an embodiment of the present disclosure.

FIG. 3 is a flowchart showing a process for producing BMPD in accordancewith an embodiment of the present disclosure.

FIG. 4 is a graph showing catalyst productivity for catalysts containingBMPD, the BMPD produced by way of different processes.

FIG. 5 is a graph showing xylene solubles for propylene-based polymersproduced by catalysts containing BMPD, the BMPD produced by differentprocesses.

FIG. 6 is a graph showing the bulk density of propylene-based polymerparticles produced from catalysts containing BMPD, the BMPD produced bydifferent processes.

DETAILED DESCRIPTION

The present disclosure is directed to the production of substitutedphenylene aromatic diester. The compound 5-tert-butyl-3-methylcatechol(or “BMC”) is found to be an effective precursor for the production ofthe substituted phenylene aromatic diester,5-tert-butyl-3-methyl-1,2-phenylene dibenzoate (or “BMPD”). BMPD is aneffective internal electron donor in Ziegler-Natta catalysts for olefinpolymerization. The processes disclosed herein advantageously provideeconomical (time, resource, production, and monetary economies),simplified, up-scalable, pathways for BMPD synthesis with yieldsacceptable for commercial/industrial application thereof.

The compound 5-tert-butyl-3-methylcatechol (BMC) has the structure (I)provided below.

BMC is an effective precursor in the production of5-tert-butyl-3-methyl-1,2-phenylene dibenzoate (BMPD). BMPD has thestructure (II) provided below.

Synthetic pathways for BMC and BMPD are known. Nonlimiting examples ofsuitable production for BMC and/or BMPD are provided in U.S. patentapplication Ser. No. 12/651,142 filed on Dec. 31, 2009 and U.S. patentapplication No. 61/468,928 filed on Mar. 29, 2011, the entire content ofeach application incorporated by reference herein.

1. Liquid BMPD Synthesis

The present disclosure provides a process. In an embodiment, a processfor producing 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate (BMPD) isprovided and includes combining, under reaction conditions in a reactionmixture, 5-tert-butyl-3-methylcatechol (BMC), triethylamine, benzoylchloride, and a water insoluble solvent. The process further includesforming a liquid BMPD product in the reaction mixture.

As used herein, “reaction conditions,” are temperature, pressure,reactant concentrations, solvent concentrations, reactantmixing/addition parameters, and/or other conditions within a reactionvessel that promote reaction between the reagents and formation of theresultant product.

A “water insoluble solvent,” as used herein, is a liquid that isimmiscible, or substantially immiscible, with water. When mixed withwater, the water insoluble solvent phase separates from the water. In anembodiment, the water insoluble solvent has a solubility in water lessthan 10 g/100 g water at standard temperature and pressure. Nonlimitingexamples of suitable water insoluble solvent include toluene, ethylacetate, orthochlorotoluene, chlorobenzene, and combinations thereof.

The BMC, triethylamine, benzoyl chloride and water insoluble solvent maybe added to the reaction vessel in any order as desired. In anembodiment, the BMC is added to the water insoluble solvent in thereaction vessel. Triethylamine is subsequently added and the reactionmixture is cooled to a temperature from 0° C. to 5° C.

In an embodiment, the benzoyl chloride is added to the reaction vesselcontaining BMC, triethylamine, and the water insoluble solvent. Duringbenzoyl chloride addition, the temperature of the reaction mixture ismaintained at less than or equal to 20° C.

The benzoyl chloride reacts with the BMC to form5-tert-butyl-3-methyl-1,2-phenylene dibenzoate (BMPD). The triethylamineabsorbs HCl, a by-product of the reaction. The BMPD is a liquid productin the reaction mixture. In other words, the BMPD is soluble in thewater insoluble solvent.

In an embodiment, the process includes adding water to the reactionmixture and washing the liquid BMPD product with the water. The wash isperformed by mixing the water with the reaction mixture by way ofstirring and/or agitation. The water insoluble solvent is insoluble inthe water. Thus, the liquid BMPD product remains dissolved in the waterinsoluble solvent during the water wash, the BMPD product remaining inthe liquid phase. Bounded by no particular theory, addition of the waterquenches the reaction, removes contaminants and/or unreacted reagentsfrom the liquid BMPD product and/or the reaction mixture; removes ionicimpurities and/or ionic by-products from the liquid BMPD product and/orthe reaction mixture; and purifies or otherwise cleanses the liquid BMPDproduct.

In an embodiment, the process includes separating the liquid BMPDproduct from the water. The water/reaction mixture combination is a twophase system having an aqueous (water) phase and a nonaqueous phase. Thewater/reaction mixture combination is allowed to phase separate. Theaqueous phase is then removed from the nonaqueous phase. Separation isperformed by way of decantation.

In an embodiment, the process includes concentrating the liquid BMPDproduct, and forming a solid BMPD product. Concentration from a liquidBMPD product to a solid BMPD product may occur by way of filtration,evaporation (rotoevaporation), and combinations thereof.

In an embodiment, the process includes purifying the solid BMPD product.Purification includes hydrocarbon washing (heptane) the solid BMPDproduct to remove organic by-products/impurities/solvents and optionaldrying. In an embodiment, the process includes purifying the BMPD, andforming a BMPD composition composed of 98 wt %, or greater than 98 wt %,or greater than 99 wt %, to 99.9 wt % BMPD.

The foregoing process advantageously reduces process steps. Utilizationof the water insoluble solvent during BMPD synthesis advantageouslyeliminates the necessity to isolate and retrieve BMPD precipitate(solid) from the reaction mixture. The present process avoids a solidproduct in the reaction mixture thereby eliminating the need forretrieval of a crude solid reaction product from the reaction mixtureand subsequent dissolution and re-crystallization of the crude productto yield a purified product. The present process yields a liquid BMPDproduct that is advantageously washed as a liquid. The present processhas a single reduction to solid phase, i.e., the concentration step(FIG. 2) or no reduction to solid phase (FIG. 3). Accordingly, thepresent process requires no dissolution step and/or re-crystallizationstep. The present process advantageously reduces the number ofproduction steps, reducing production equipment, reducing man hoursrequired to produce the BMPD, and/or reducing the reagents required forBMPD production.

In addition to BMC, the processes disclosed herein may utilize a widefamily of substituted catechol as a starting reagent. Catechols suitableas starting reagents in the present processes are catechols substitutedat the 4-position, such as 4-methyl catechol and/or 4-tert-butylcatechol which correspondingly produce 4-methyl 1,2-phenylene dibenzoateand 4-tert-butyl 1,2-phenylene dibenzoate. Catechols with othersubstitution patterns can also be used.

2. Procatalyst Production

The present disclosure provides another process. In an embodiment, aprocess for producing a procatalyst composition is provided and includescombining, under reaction conditions in a first reaction mixture, awater insoluble solvent, BMC, triethylamine, and benzoyl chloride. TheBMC and benzoyl chloride react to form a liquid BMPD product (in thewater insoluble solvent) in the first reaction mixture. The processfurther includes adding, under reaction conditions, the liquid BMPDproduct to a second reaction mixture. The second reaction mixtureincludes a procatalyst precursor, a halogenating agent, and optionallychlorobenzene and/or toluene and/or orthochlorotoluene. The processfurther includes forming a solid procatalyst composition.

In an embodiment, the process includes adding to the first reactionmixture the water insoluble solvent selected from toluene, ethylacetate, orthochlorotoluene, chlorobenzene, and combinations thereof.

In an embodiment, the process includes adding the water insolublesolvent chlorobenzene to the first reaction mixture.

In an embodiment, the water insoluble solvent in the first reactionmixture and the solvent in the second reaction mixture is chlorobenzene.Having the common solvent chlorobenzene across the first reactionmixture and the second reaction mixture yields production efficiency.Production efficiency occurs because the reaction product, namely theliquid BMPD product, of the first reaction mixture is ready to add tothe second reaction mixture without further refinement or processing.The liquid BMPD is a liquid in both the first reaction mixture and thesecond reaction mixture.

In an embodiment, the second reaction mixture does not includechlorobenzene. Rather, the chlorobenzene from the first reaction mixtureis utilized as the solvent in the second reaction mixture.

In an embodiment, the process includes adding the water insolublesolvent orthochlorotoluene to the first reaction mixture.

In an embodiment, the water insoluble solvent in the first reactionmixture is orthochlorotoluene and the solvent in the second reactionmixture is chlorobenzene. The use of orthochlorotoluene (OCT) as thesolvent in the first reaction mixture is particularly advantageousbecause the OCT is subsequently used as a separation agent whenrecovering the chlorobenzene solvent and TiCl₄ of the second reactionmixture and the byproducts formed during chlorination of the procatalystprecursor.

The second reaction mixture includes a procatalyst precursor. Theprocatalyst precursor is a magnesium moiety compound (MagMo), a mixedmagnesium titanium compound (MagTi), or a benzoate-containing magnesiumchloride compound (BenMag). In an embodiment, the procatalyst precursoris a magnesium moiety (“MagMo”) precursor. The “MagMo precursor”contains magnesium as the sole metal component. The MagMo precursorincludes a magnesium moiety. Nonlimiting examples of suitable magnesiummoieties include anhydrous magnesium chloride and/or its alcohol adduct,magnesium alkoxide or aryloxide, mixed magnesium alkoxy halide, and/orcarboxylated magnesium dialkoxide or aryloxide. In one embodiment, theMagMo precursor is a magnesium di (C₁₋₄)alkoxide. In a furtherembodiment, the MagMo precursor is diethoxymagnesium.

In an embodiment, the procatalyst precursor is a mixedmagnesium/titanium compound (“MagTi”). The “MagTi precursor” has theformula Mg_(d)Ti(OR^(e))_(f)X_(g) wherein R^(e) is an aliphatic oraromatic hydrocarbon radical having 1 to 14 carbon atoms or COR′ whereinR′ is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbonatoms; each OR^(e) group is the same or different; X is independentlychlorine, bromine or iodine, preferably chlorine; d is 0.5 to 56, or 2to 4; f is 2 to 116 or 5 to 15; and g is 0.5 to 116, or 1 to 3. Theprecursors are prepared by controlled precipitation through removal ofan alcohol from the reaction mixture used in their preparation. In anembodiment, a reaction medium comprises a mixture of an aromatic liquid,especially a chlorinated aromatic compound, most especiallychlorobenzene, with an alkanol, especially ethanol. Suitablehalogenating agents include titanium tetrabromide, titaniumtetrachloride or titanium trichloride, especially titaniumtetrachloride. Removal of the alkanol from the solution used in thehalogenation, results in precipitation of the solid precursor, havingespecially desirable morphology and surface area. Moreover, theresulting precursors are particularly uniform in particle size.

In an embodiment, the procatalyst precursor is a benzoate-containingmagnesium chloride material (“BenMag”). As used herein, a“benzoate-containing magnesium chloride” (“BenMag”) can be a procatalyst(i.e., a halogenated procatalyst precursor) containing a benzoateinternal electron donor. The BenMag material may also include a titaniummoiety, such as a titanium halide. The benzoate internal donor is labileand can be replaced by the BMPD or other electron donors duringprocatalyst and/or catalyst synthesis. Nonlimiting examples of suitablebenzoate groups include ethyl benzoate, methyl benzoate, ethylp-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate,ethyl p-chlorobenzoate. In one embodiment, the benzoate group is ethylbenzoate. Nonlimiting examples of suitable BenMag procatalyst precursorsinclude catalysts of the trade names SHAC™ 103 and SHAC™ 310 availablefrom The Dow Chemical Company, Midland, Mich. In an embodiment, theBenMag procatalyst precursor may be a product of halogenation of anyprocatalyst precursor (i.e., a MagMo precursor or a MagTi precursor) inthe presence of a benzoate compound.

The second reaction mixture includes a halogenating agent. A“halogenating agent,” as used herein, is a compound that converts theprocatalyst precursor into a halide form. The second reaction mixturemay also include a titanating agent. A “titanating agent,” as usedherein, is a compound that provides the catalytically active titaniumspecies. Halogenation and titanation convert the magnesium moietypresent in the procatalyst precursor into a magnesium halide supportupon which the titanium moiety (such as a titanium halide) is deposited.

In an embodiment, the halogenating agent is a titanium halide having theformula Ti(OR^(e))_(f)X_(h) wherein R^(e) and X are defined as above, fis an integer from 0 to 3; h is an integer from 1 to 4; and f+h is 4. Inthis way, the titanium halide is simultaneously the halogenating agentand the titanating agent. In a further embodiment, the halogenatingagent is TiCl₄ and halogenation occurs by way of chlorination of theprocatalyst precursor with the TiCl₄. TiCl₄ can simultaneously be achlorinating agent and a titanating agent. The chlorination (andtitanation) is conducted in the presence of chlorobenzene, the solvent.In an embodiment, the chlorination (and titanation) are conducted by useof a mixture of 40-60 vol % TiCl₄ in chlorobenzene, or 45-55 vol % TiCl₄in chlorobenzene.

The manner in which the procatalyst precursor, the halogenating agentand the BMPD are contacted and/or added to the second reaction mixturemay be varied as desired. In an embodiment, the procatalyst precursor isfirst contacted with a mixture of TiCl₄ in chlorobenzene. The resultingmixture is stirred and may be heated if desired. Next, the internalelectron donor (the liquid BMPD product) is added to the same reactionmixture without isolating or recovering the procatalyst precursor fromthe second reaction mixture.

In an embodiment, the procatalyst precursor is contacted with the liquidBMPD product before addition of the TiCl₄.

In an embodiment, the procatalyst precursor, the BMPD, and the TiCl₄ areadded to the second reaction mixture simultaneously or substantiallysimultaneously.

In the second reaction mixture, the TiCl₄ contacts and chlorinates theprocatalyst precursor and converts the procatalyst precursor to a solidprocatalyst in the presence of the BMPD, the internal electron donor.The TiCl₄ converts the magnesium moiety present in the procatalystprecursor into a magnesium chloride support upon which the titaniummoiety (such as a titanium halide) is deposited. As used herein, an“internal electron donor” is a compound added during formation of theprocatalyst composition, the internal electron donor donating a pair ofelectrons to one or more metals present in the resultant procatalystcomposition. Not wishing to be bound by any particular theory, it isbelieved that during chlorination the internal electron donor BMPD (1)regulates the position of titanium on the magnesium-based support, (2)facilitates conversion of the magnesium and titanium moieties intorespective halides and (3) regulates the crystallite size of themagnesium halide support during conversion. Thus, provision of the BMPDin the second reaction mixture yields a procatalyst composition withenhanced stereoselectivity.

Contact times of the procatalyst precursor with the liquid BMPD are atleast 10 minutes, or at least 15 minutes, or at least 20 minutes, or atleast 1 hour at a temperature from at least 25° C., or at least 50° C.,or at least 60° C. up to a temperature of 150° C., or up to 120° C., orup to 115° C., or up to 110° C.

In an embodiment, the second reaction mixture is heated to a temperatureless than 115° C., or from about 90° C. to less than or equal to 100° C.during chlorination. Applicants have surprisingly discovered thatchlorination of the procatalyst precursor and the BMPD at a temperaturerange less than 115° C., and from 90° C. to less than or equal to 100°C. in particular, unexpectedly produces a procatalyst composition withimproved selectivity. This result is unexpected because lowering thehalogenation temperature during preparation of conventional procatalystcompositions reduces or otherwise diminishes procatalyst selectivity. Inparticular, it is known that reducing the halogenation temperature below115° C. during preparation/halogenation of a phthalate-based internalelectron donor (such as diisobutylphthalate) diminishes or otherwisedegrades the selectivity for the phthalate-based procatalystcomposition.

In an embodiment, the process includes adding the first reaction mixturedirectly to the second reaction mixture. The common solvent(chlorobenzene and/or toluene and/or OCT) across the first reactionmixture and the second reaction mixture advantageously enables the firstreaction mixture to be added directly to the second reaction mixturewithout refinement and/or processing. The common solvent (chlorobenzeneand/or toluene and/or OCT) promotes direct and/or immediate transfer ofthe liquid BMPD product without the need for any intermediate steps. Theuse of a mixture of solvents can also be advantageous as a solventmixture may improve increase the efficiency of the TiCl₄ and solventrecovery systems/procedures.

The term “directly adding,” or “direct addition,” or like term as usedherein is the addition of the first reaction mixture to the secondreaction mixture without any other process steps involving the firstreaction mixture. In other words, the first reaction mixture is directlyadded “as is” to the second reaction mixture.

The chlorination procedure may be repeated one, two, three, or moretimes as desired, either alone or in the presence of the liquid BMPD. Inan embodiment, the resulting solid material (procatalyst material) isrecovered from the second reaction mixture and contacted one or moretimes with additional TiCl₄ in the absence (or in the presence) of theadditional liquid BMPD product with chlorobenzene as the solvent.

In an embodiment, the process includes second halogenating the solidprocatalyst composition with an additional amount of TiCl₄, optionallyin the presence of additional liquid BMPD product. The solid procatalystcomposition may or may not be isolated from the second reaction mixtureprior to the second halogenation.

In an embodiment, the process includes third halogenating the solidprocatalyst composition with another additional amount of TiCl₄,optionally in the presence of the liquid BMPD product. The solidprocatalyst composition may or may not be isolated prior to the thirdhalogenation.

The foregoing process(es) convert the procatalyst precursor and the BMPDinto a combination of a magnesium moiety and a titanium moiety, intowhich the BMPD is incorporated. The magnesium moiety is a magnesiumchloride. The titanium moiety is a titanium chloride.

After the foregoing one or more halogenation (chlorination) procedures,the resulting solid procatalyst composition is separated from thereaction mixture, by filtering for example, to produce a moist filtercake. The moist filter cake may then be rinsed or washed with a liquiddiluent to remove unreacted TiCl₄ and may be dried to remove residualliquid, if desired. Typically the resultant solid procatalystcomposition is washed one or more times with a “wash liquid,” which is aliquid hydrocarbon such as an aliphatic hydrocarbon such as isopentane,isooctane, isohexane, hexane, pentane, or octane. The solid procatalystcomposition then can be separated and dried or slurried in ahydrocarbon, especially a relatively heavy hydrocarbon such as mineraloil for further storage or use.

In an embodiment, the resulting solid procatalyst composition has atitanium content of from about 1.0 percent by weight to about 6.0percent by weight, based on the total solids weight, or from about 1.5percent by weight to about 4.5 percent by weight, or from about 2.0percent by weight to about 3.5 percent by weight. The weight ratio oftitanium to magnesium in the solid procatalyst composition is suitablybetween about 1:2 and about 1:160, or between about 1:2.5 and about1:50, or between about 1:3 and 1:30, or 1:3.5. In an embodiment, theBMPD may be present in the procatalyst composition in a molar ratio ofBMPD to magnesium of from about 0.005:1 to about 1:1, or from about0.01:1 to about 0.4:1. Weight percent is based on the total weight ofthe procatalyst composition.

In an embodiment, the molar ratio of BMPD to Mg is 0.06:1.

Not wishing to be bound by any particular theory, it is believed that(1) further halogenation by contacting the previously formed solidprocatalyst composition with additional titanium chloride, and/or (2)further washing the previously formed procatalyst composition withchlorobenzene at an elevated temperature (100° C.-150° C.), results indesirable modification of the procatalyst composition, possibly byremoval of certain inactive or undesired metal compounds that aresoluble in the foregoing solvent.

The present process for producing a procatalyst composition may comprisetwo or more embodiments disclosed herein.

3. Polymerization

Any of the foregoing procatalyst compositions may be used in an olefinpolymerization process. In an embodiment, a polymerization process isprovided and includes contacting, under polymerization conditions, theprocatalyst composition BMPD, a cocatalyst, optionally an externalelectron donor with propylene and optionally one or more olefins. Thepolymerization forms a propylene-based polymer (propylene homopolymer)having less than 6 wt %, or less than 4 wt %, or less than 3 wt %, orless than 2.5 wt %, or less than 1 wt %, or from 0.1 wt % to less than 4wt %, or from 0.1 wt % to less than 2.5 wt % xylene solubles (XS).Weight percent XS is based on the total weight of the polymer.

As used herein, a “cocatalyst” is a substance capable of converting theprocatalyst to an active polymerization catalyst. The cocatalyst mayinclude hydrides, alkyls, or aryls of aluminum, lithium, zinc, tin,cadmium, beryllium, magnesium, and combinations thereof. In anembodiment, the cocatalyst is a hydrocarbyl aluminum compoundrepresented by the formula R_(n)AlX_(3-n) wherein n=1 2, or 3, R is analkyl, and X is a halide or alkoxide. In an embodiment, the cocatalystis selected from trimethylaluminum, triethylaluminum,triisobutylaluminum, and tri-n-hexylaluminum.

Nonlimiting examples of suitable hydrocarbyl aluminum compounds are asfollows: methylaluminoxane, isobutylaluminoxane, diethylaluminumethoxide, diisobutylaluminum chloride, tetraethyldialuminoxane,tetraisobutyldialuminoxane, diethylaluminum chloride, ethylaluminumdichloride, methylaluminum dichloride, dimethylaluminum chloride,triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride,di-n-hexylaluminum hydride, isobutylaluminum dihydride, n-hexylaluminumdihydride, diisobutylhexylaluminum, isobutyldihexylaluminum,trimethylaluminum, triethylaluminum, tri-n-propylaluminum,triisopropylaluminum, tri-n-butylaluminum, tri-n-octylaluminum,tri-n-decylaluminum, tri-n-dodecylaluminum, diisobutylaluminum hydride,and di-n-hexylaluminum hydride.

In an embodiment, the cocatalyst is triethylaluminum. The molar ratio ofaluminum to titanium is from about 5:1 to about 500:1, or from about10:1 to about 200:1, or from about 15:1 to about 150:1, or from about20:1 to about 100:1. In another embodiment, the molar ratio of aluminumto titanium is about 45:1.

As used herein, an “external electron donor” (or “EED”) is a compoundadded independent of procatalyst formation and includes at least onefunctional group that is capable of donating a pair of electrons to ametal atom. Bounded by no particular theory, it is believed thatprovision of one or more external electron donors in the catalystcomposition affects the following properties of the formant polymer:level of tacticity (i.e., xylene soluble material), molecular weight(i.e., melt flow), molecular weight distribution (MWD), melting point,and/or oligomer level.

In an embodiment, the EED is a silicon compound having the generalformula (II):

SiR_(m)(OR′)_(4-m)  (II)

wherein R independently each occurrence is hydrogen or a hydrocarbyl oran amino group, optionally substituted with one or more substituentscontaining one or more Group 14, 15, 16, or 17 heteroatoms. R containsup to 20 atoms not counting hydrogen and halogen. R′ is a C₁₋₂₀ alkylgroup, and m is 0, 1, 2, or 3. In an embodiment, R is C₆₋₁₂ aryl, alkylor alkylaryl, C₃₋₁₂ cycloalkyl, C₃₋₁₂ branched alkyl, or C₃₋₁₂ cyclicamino group, R′ is C₁₋₄ alkyl, and m is 1 or 2.

In an embodiment, the silane composition is dicyclopentyldimethoxysilane(DCPDMS), methylcyclohexyldimethoxysilane (MChDMS), orn-propyltrimethoxysilane (NPTMS), and any combination thereof.

The polymerization reaction forms a propylene homopolymer or a propylenecopolymer. Optionally, one or more olefin monomers can be introducedinto a polymerization reactor along with the propylene to react with theprocatalyst, cocatalyst, and EED and to form a polymer, or a fluidizedbed of polymer particles. Nonlimiting examples of suitable olefinmonomers include ethylene, C₄₋₂₀ α-olefins, such as 1-butene, 1-pentene,1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodeceneand the like.

In an embodiment, the polymerization process may include apre-polymerization step and/or a pre-activation step.

In an embodiment, the process includes mixing the external electrondonor with the procatalyst composition. The external electron donor canbe complexed with the cocatalyst and mixed with the procatalystcomposition (pre-mixed) prior to contact between the catalystcomposition and the olefin. In another embodiment, the external electrondonor can be added independently to the polymerization reactor.

In an embodiment, the process includes forming a propylene-based polymer(propylene homopolymer or propylene copolymer) containing the BMPD. Thepropylene-based polymer has one or more of the following properties:

a melt flow rate (MFR) from about 0.01 g/10 min to about 800 g/10 min,or from about 0.1 g/10 min to about 200 g/10 min, or from about 0.5 g/10min to about 150 g/10 min;

a xylene solubles content from about 0.1 wt % to about 11 wt %, or fromabout 0.1 wt % to about wt %, or from about 0.1 wt % to about 4 wt %, orfrom 0.1 wt % to less than 2.5 wt %;

a polydispersity index (PDI) from about 3.8 to about 15.0, or from about4.0 to about 10, or from about 4.0 to about 8.0; and/or

particles thereof with a bulk density greater than 0.28 g/cc to about0.50 g/cc.

The propylene-based polymer may comprise two or more embodimentsdisclosed herein.

In an embodiment, the procatalyst composition and/or the polymerproduced therefrom are/is phthalate-free or are/is otherwise void ordevoid of phthalate and derivatives thereof.

The disclosure provides another process. In an embodiment, a process isprovided and includes forming a liquid BMPD product and adding, underreaction conditions, the liquid BMPD product to a procatalyst precursor,a halogenating agent, and chlorobenzene to form a solid procatalystcomposition. The process further includes contacting an olefin, underpolymerization conditions, with the solid procatalyst composition, acocatalyst, and an external electron donor and forming an olefin-basedpolymer.

In an embodiment, the olefin is propylene. The process includes forminga propylene homopolymer polymer having a xylene solubles content from0.5 wt %, or 0.8 wt %, or 1.0 wt %, to 6.0 wt %, or 5.5 wt %, or 5.0 wt%, or 4.5 wt %, or 4.0 wt %.

In an embodiment, the olefin is propylene and ethylene. The processincludes forming a propylene/ethylene copolymer having 0.5 wt % to 0.6wt % units derived from ethylene and a xylene solubles content from 3.5wt % to 3.8 wt %.

In an embodiment, the olefin is propylene and ethylene. The processincludes forming a propylene/ethylene copolymer having 3.2 wt % unitsderived from ethylene and a xylene solubles content from 4.8 wt % to 5.9wt %.

In an embodiment, the olefin is propylene and ethylene. The processincludes forming a propylene/ethylene copolymer having 5.7 wt % unitsderived from ethylene and a xylene solubles content of 10.5 wt %.

In an embodiment, the olefin is propylene. The process includes formingparticles of a propylene homopolymer, the particles having a bulkdensity from 0.27 g/cm³ (18 lbs/ft³) to 0.42 g/cm³ (26 lbs/ft³).

DEFINITIONS

All references to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2003. Also, any references to a Group or Groups shall be tothe Groups or Groups reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. Unless stated to thecontrary, implicit from the context, or customary in the art, all partsand percents are based on weight. For purposes of United States patentpractice, the contents of any patent, patent application, or publicationreferenced herein are hereby incorporated by reference in their entirety(or the equivalent US version thereof is so incorporated by reference),especially with respect to the disclosure of synthetic techniques,definitions (to the extent not inconsistent with any definitionsprovided herein) and general knowledge in the art.

Any numerical range recited herein, includes all values from the lowervalue to the upper value, in increments of one unit, provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent, or a value of a compositional or a physical property, suchas, for example, amount of a blend component, softening temperature,melt index, etc., is between 1 and 100, it is intended that allindividual values, such as, 1, 2, 3, etc., and all subranges, such as, 1to 20, 55 to 70, 197 to 100, etc., are expressly enumerated in thisspecification. For values which are less than one, one unit isconsidered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. These areonly examples of what is specifically intended, and all possiblecombinations of numerical values between the lowest value and thehighest value enumerated, are to be considered to be expressly stated inthis application. In other words, any numerical range recited hereinincludes any value or subrange within the stated range. Numerical rangeshave been recited, as discussed herein, reference melt index, melt flowrate, and other properties.

The term “alkyl,” as used herein, refers to a branched or unbranched,saturated or unsaturated acyclic hydrocarbon radical. Nonlimitingexamples of suitable alkyl radicals include, for example, methyl, ethyl,n-propyl, i-propyl, 2-propenyl (or allyl), vinyl, n-butyl, t-butyl,i-butyl (or 2-methylpropyl), etc. The alkyls have 1 and 20 carbon atoms.

The term “aryl,” as used herein, refers to an aromatic substituent whichmay be a single aromatic ring or multiple aromatic rings which are fusedtogether, linked covalently, or linked to a common group such as amethylene or ethylene moiety. The aromatic ring(s) may include phenyl,naphthyl, anthracenyl, and biphenyl, among others. The aryls have 1 and20 carbon atoms.

The term “composition,” as used herein, includes a mixture of materialswhich comprise the composition, as well as reaction products anddecomposition products formed from the materials of the composition.

The term “comprising,” and derivatives thereof, is not intended toexclude the presence of any additional component, step or procedure,whether or not the same is disclosed herein. In order to avoid anydoubt, all compositions claimed herein through use of the term“comprising” may include any additional additive, adjuvant, or compoundwhether polymeric or otherwise, unless stated to the contrary. Incontrast, the term, “consisting essentially of” excludes from the scopeof any succeeding recitation any other component, step or procedure,excepting those that are not essential to operability. The term“consisting of” excludes any component, step or procedure notspecifically delineated or listed. The term “or”, unless statedotherwise, refers to the listed members individually as well as in anycombination.

The term “ethylene-based polymer,” as used herein, refers to a polymerthat comprises a majority weight percent polymerized ethylene monomer(based on the total amount of polymerizable monomers), and optionallymay comprise at least one polymerized comonomer.

The term “olefin-based polymer” is a polymer containing, in polymerizedform, a majority weight percent of an olefin, for example ethylene orpropylene, based on the total weight of the polymer. Nonlimitingexamples of olefin-based polymers include ethylene-based polymers andpropylene-based polymers.

The term “polymer” is a macromolecular compound prepared by polymerizingmonomers of the same or different type. “Polymer” includes homopolymers,copolymers, terpolymers, interpolymers, and so on. The term“interpolymer” means a polymer prepared by the polymerization of atleast two types of monomers or comonomers. It includes, but is notlimited to, copolymers (which usually refers to polymers prepared fromtwo different types of monomers or comonomers, terpolymers (whichusually refers to polymers prepared from three different types ofmonomers or comonomers), tetrapolymers (which usually refers to polymersprepared from four different types of monomers or comonomers), and thelike.

The term, “propylene-based polymer,” as used herein, refers to a polymerthat comprises a majority weight percent polymerized propylene monomer(based on the total amount of polymerizable monomers), and optionallymay comprise at least one polymerized comonomer.

The term “substituted alkyl,” as used herein, refers to an alkyl as justdescribed in which one or more hydrogen atom bound to any carbon of thealkyl is replaced by another group such as a halogen, aryl, substitutedaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, halogen, haloalkyl, hydroxy, amino, phosphido, alkoxy,amino, thio, nitro, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl, trifluoromethyl and the like.

The term “substituted phenylene aromatic diester” includes substituted1,2-phenylene aromatic diester, substituted 1,3-phenylene aromaticdiester, and substituted 1,4-phenylene aromatic diester. In anembodiment, the substituted phenylene diester is a 1,2-phenylenearomatic diester with the structure (A) below:

wherein R₁-R₁₄ are the same or different. Each of R₁-R₁₄ is selectedfrom a hydrogen, substituted hydrocarbyl group having 1 to 20 carbonatoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms,an alkoxy group having 1 to 20 carbon atoms, a heteroatom, andcombinations thereof. At least one of R₁-R₁₄ is not hydrogen.

Test Methods

¹H nuclear magnetic resonance (NMR) data is obtained via a Brüker 400MHz spectrometer in CDCl₃ (in ppm).

Melt flow rate (MFR) is measured in accordance with ASTM D 1238 testmethod and 230° C. with a 2.16 kg weight for propylene based polymer.

Bulk density is determined in accordance with ASTM D 1895 procedure B,and is measured as follows:

a. Fill a 4 oz tin can (about 30 grams) with polymer sample.

b. Pour resin through funnel into a pre-weighed metal cup (201 g/100 cc)until resin overfills the cup.

c. Level off the resin to the top of the cup using a large spatula. Donot shake the cup or pack the polymer in.

d. Weigh the cup with the polymer and subtract the weight of the cup.

e. The bulk density=g polymer/100 cc.

Xylene Solubles (XS) is the weight percent of resin (based on the totalweight of the resin) that stays in the solution after the resin isdissolved in hot xylene and the solution is allowed to cool to 25° C. XSis measured using a ¹H NMR method as described in U.S. Pat. No.5,539,309, the entire content of which is incorporated herein byreference. XS may also be measured by flow injection polymer analysisusing a Viscotek ViscoGEL H-100-3078 column with THF mobile phaseflowing at 1.0 ml/min. The column is coupled to a Viscotek Model 302Triple Detector Array, with light scattering, viscometer andrefractometer detectors operating at 45° C. Instrument calibration ismaintained with Viscotek PolyCAL™ polystyrene standards.

By way of example, and not limitation, examples of the presentdisclosure are provided.

EXAMPLES A. BMPD

Comparative Sample 1. BMPD is prepared and purified according to theflowchart shown in FIG. 1 and is designated “refined BMPD.”

Example 1

Liquid BMPD product is prepared from toluene and concentrated to solidaccording to the flowchart shown in FIG. 2 and is designated as“BMPD/T.”

Example 2

Liquid BMPD product is prepared from ethyl acetate and concentrated tosolid according to the flowchart shown in FIG. 2 and is designated as“BMPD/EtOAc.”

Example 3

Liquid BMPD product is prepared in chlorobenzene according to theflowchart shown in FIG. 3 and is designated as “BMPD/CB.”

B. Catalyst Composition

Each of the four BMPD samples above is used as an internal electrondonor in a respective procatalyst composition. The solid BMPD samplesprepared in Examples 1 and (above) are dissolved in chlorobenzene (CB)to 0.88 M solution. The BMPD solution of Example 3 is used as prepared.

The procatalyst compositions are prepared in fritted vessels that arestirred and electrically heated. 60 ml of 50 vol % TiCl₄/CB are added tothe vessels at room temperature. Three grams of 27-μm MagTi precursorare added to the solution during stirring forming a slurry, and aftertwo minutes the slurry is heated to 100° C. over a 50 minute period. Asolution containing 1.03 grams of BMPD is added to the slurry when thetemperature reaches 75° C. The reaction proceeds at 100° C. for minutes,after which the first hot step is terminated by draining the solventthrough the bottom of the frit in the absence of stirring.

An additional 60 ml of TiCl₄/CB are then added and the stirring isresumed. A solution containing 0.47 grams of BMPD donor is added. Theslurry is heated to 115° C. and held for 30 minutes, and then filteredagain (second hot step).

For the third hot step, 60 ml of TiCl₄/CB solution is added and theslurry is heated to 115° C. for 30 minutes. After the third filtrationof TiCl₄/CB, the solid catalyst is rinsed and filtered three times atroom temperature with 60 ml of isooctane. The wet catalyst cake is thendried to a free flowing powder under a nitrogen flow. The dry powderprocatalyst composition is dispersed to a 5 wt % slurry in mineral oilfor storage and handling.

C. Polymerization

Each of the four procatalyst compositions are polymerized in liquidpropylene. The catalyst productivity and polymer xylene solubles (ameasure of stereoregularity in the polymer) and settled bulk densityobtained with the catalysts prepared by alternate routes (FIGS. 2-3) andfrom the original method are comparable to those prepared from theoriginal method with full purification (refined BMPD) (FIG. 1).

Liquid propylene is polymerized under reaction conditions in a 1-gallonautoclave reactor. Each procatalyst composition is polymerized in liquidpropylene in a 1-gallon autoclave. The reactor is charged with 1375 g ofpropylene and 3000 standard cm³ of hydrogen and brought to 62° C. Theprocatalyst composition in the amount of 0.10 ml of 5-wt % slurry isprecontacted with 7.2 ml of 0.27-M triethyl aluminum in isooctane andwith 20 μl of dicyclopentyldimethoxysilane for minutes to form thecatalyst composition. The catalyst composition is then injected into thereactor at 62° C. to initiate polymerization. All catalyst componentsare flushed into the reactor with isooctane using a high-pressurecatalyst injection pump. After the exotherm, the temperature iscontrolled to 67° C. for the duration of the one-hour runs.

The reaction of BMC and BC with the triethylamine scavenger createsbyproducts in the desired BMPD product. It was expected that removal ofreaction byproducts would require extensive purification in order torecover a BMPD grade of sufficient purity to be used in procatalystproduction. However, it is unexpectedly discovered that the BMPDrecovery process is simplified (resulting in shorter production times,lower raw material costs, and less waste generation) by way of theliquid BMPD product with the use of the water insoluble solvent.

Furthermore, the BMPD production can take place in solvents that can bedirectly used in the production of the procatalyst composition. Directaddition of the liquid BMPD product advantageously eliminates processsteps by avoiding the need to crystallize and separate the BMPD as asolid.

FIG. 4 shows catalyst efficiency (productivity). The productivity forcatalyst compositions containing BMPD made by way of procedures ofExamples 1-3 exhibit catalyst efficiency from 41 kg/g to 53 kg/g.

FIG. 5 shows xylene solubles content for propylene homopolymer made fromcatalysts containing BMPD produced by way of the procedures ofcomparative sample 1 and Examples 1-3. For propylene homopolymer made byway of Examples 1-3, the average xylene solubles content is from 2.1 wt% to 2.5 wt %.

FIG. 6 shows polymer settled bulk density for polymers made fromcatalysts containing BMPD produced by way of the procedures ofcomparative sample 1 and Examples 1-3. The average settled bulk densityfor propylene homopolymer made by way of Examples 1-3 is from 0.375g/cm³ to 0.40 g/cm³.

It is specifically intended that the present disclosure not be limitedto the embodiments and illustrations contained herein, but includemodified forms of those embodiments including portions of theembodiments and combinations of elements of different embodiments ascome within the scope of the following claims.

What is claimed is:
 1. A process comprising: combining, under reactionconditions in a first reaction mixture, a first water insoluble solvent,BMC, triethylamine, and benzoyl chloride and forming a liquid BMPDproduct; adding, under reaction conditions, the first reaction mixtureincluding the liquid BMPD product directly to a second reaction mixturecomprising a procatalyst precursor, a halogenating agent, and a secondwater insoluble solvent; and forming a solid procatalyst composition. 2.The process of claim 1 comprising adding to the first reaction mixture awater insoluble solvent selected from the group consisting of toluene,ethyl acetate, orthochlorotoluene, chlorobenzene, and combinationsthereof.
 3. The process of claim 2 comprising adding to the secondreaction mixture a water insoluble solvent selected from the groupconsisting of toluene, ethyl acetate, orthochlorotoluene, chlorobenzene,and combinations thereof.
 4. The process of claim 3, wherein the firstand second water insoluble solvents are the same.
 5. The process ofclaim 1 comprising adding to the first and second reaction mixture thewater insoluble solvent orthochlorotoluene.
 6. The process of claim 1comprising adding to the first and second reaction mixture the waterinsoluble solvent chlorobenzene.
 7. A process comprising: forming aliquid BMPD product; adding, under reaction conditions, the liquid BMPDproduct to a procatalyst precursor, a halogenating agent, andchlorobenzene to form a solid procatalyst composition; contacting apropylene, under polymerization conditions, with the solid procatalystcomposition, a cocatalyst, and an external electron donor; and forming apropylene homopolymer having a xylene solubles content from 0.5 wt % to6 wt %.
 8. The process of claim 7 comprising forming the liquid BMPDproduct in a water insoluble solvent selected from the group consistingof toluene, ethyl acetate, orthochlorotoluene, chlorobenzene, andcombinations thereof.
 9. The process of claim 7 comprising forming theliquid BMPD product in the solvent orthochlorotoluene.
 10. The processof claim 7 comprising forming the liquid BMPD product in the solventorthochlorobenzene.